Formate species in the low-temperature oxidation of dimethyl ether

The oxidation of dimethyl ether (DME, 340 ppm in 10% O2) has been studied experimentally in an atmospheric pressure laminar flow reactor in the temperature range from 240 degrees C to 700 degrees C for residence times in the range 2-4 s. The influence of nitric oxide additions up to 620 ppm to the feed gases has also been investigated. Products of reaction were determined by FTIR. In the absence of NO, reaction is first detected at about 260 degrees C. The products in the low-temperature region include formaldehyde (HCHO), and formic acid (HCOOH). The addition of NO leads to the appearance of methyl formate (CH3OCHO). While the overall behaviour of the system can be explained qualitatively in terms of typical low-temperature hydrocarbon ignition, recently published chemical kinetic models for DME ignition do not allow for the formation of these formate species. We find no experimental evidence for the formation of hydroperoxymethyl formate (HPMF, HOOCH2OCHO) which is predicted by the models to be a significant stable intermediate at temperatures below 350 degrees C. Since both formic acid and methyl formate have potentially harmful health effects, these observations may have significant implications for use of DME as a diesel fuel.     

A new model of tropospheric hydroxyl radical concentrations

A chemistry model of the global troposphere is presented which focuses on the hydroxyl radical, OH. Global distributions of OH are calculated based on known chemical reaction pathways, experimentally measured values of precursor species O3, H2O, NOx (defined as NO+NO2), CO, CH4, and actinic flux (which includes the effects of cloud cover and O3 column absorption). Model grid resolution is 1 km in altitude by 10 degrees latitude, and zonally divided into land or ocean. Species are calculated as seasonal averages. Global annual mean OH in the troposphere (up to 14 km altitude) is calculated to be 9.2 x 10(5) molcm(-3) with averages of 9.8 x 10(5) in the northern hemisphere, and 8.5 x 10(5) in the southern hemisphere. Global CO and CH(4) oxidation rates by OH are calculated to be 1840 Tgyear(-1) and 580 Tgyear(-1), respectively. OH is found to be most sensitive to O3 and H2O concentrations, as well as to the photolysis rate of O3 to O1D. Sensitivity of CO and CH4 oxidation rates to cloud presence shows an inverse relationship to cloud amount and optical depth. Model results are shown to be consistent with results from two other published models.     

Oxidation of MCPA and 2,4-D by UV radiation, ozone, and the combinations UV/H2O2 and O3/H2O2

The phenoxyalkyl acid derivative herbicides MCPA (4-chloro 2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) were oxidized in ultrapure water by means of a monochromatic UV irradiation and by ozone, as well as by the combinations UV/H2O2 and O3/H2O2. In the direct photolysis of MCPA, the quantum yield at 20 degrees C was directly evaluated and a value of 0.150 mol Eins(-1) was obtained in the pH range 5-9, while a lower value of 0.41 x 10(-2) mol Eins(-1) was determined at pH=3. Similarly, for 2,4-D a value of 0.81 x 10(-2) mol Eins(-1) was deduced, independent of the pH of work. The influence of the additional presence of hydrogen peroxide was established in the combined process UV/H2O2, and the specific contribution of the radical pathway to the global photo-degradation was evaluated. The oxidation by ozone and by the combination O3/H2O2 was also studied, with the determination of the rate constants for the reactions of both herbicides with ozone and hydroxyl radicals at 20 degrees C. These rate constants for the direct reactions with ozone were 47.7 and 21.9 M(-1) s(-1) for MCPA and 2,4-D respectively, while the found values for the rate constants corresponding to the radical reactions were 6.6 x 10(9) and 5.1 x 10(9) M(-1) s(-1).     

Slow desorption of PCBs and chlorobenzenes from soils and sediments: relations with sorbent and sorbate characteristics

The kinetics of slow desorption were studied for four soils and four sediments with widely varying characteristics [organic carbon (OC) content 0.5-50%, organic matter (OM) aromatic content (7-37%)] for three chlorobenzenes and five polychlorinated biphenyls (PCBs). Slowly and very slowly desorbing fractions ranged from 1 to 50% (slow) and 3 to 40% (very slow) of the total amount sorbed, and were observed for all compounds and all soils and sediments. In spite of the wide variations in sorbate K(OW) (factor 1000) and sorbent characteristics, the rate constants of slow (k(slow), around 10(-3) h(-1)) and very slow (k(very slow), 10(-5)-10(-4) h(-1)) desorption appeared to be rather constant among the sorbates and sorbents (both within a factor of 5). There was a good correlation (r(2) above 0.9) between the distribution over the slow, very slow and rapid sediment fractions and log K(OC), indicating that sorbate hydrophobicity may be important for this distribution. No correlation could be found between sorbent characteristics [OC, N, and O in the organic matter, polarity index C/(N+O), OC aromaticity as determined by CP-MAS (13)C-NMR] and slow desorption parameters (slowly/very slowly desorbing fractions+corresponding rate constants). The absence of (1) a correlation between k(slow) and k(very slow), respectively, and OC content, and (2) the narrow range of k(slow) and k(very slow) values, indicates that intra-OM diffusion is not the mechanism of slow or very slow desorption, because on the basis of this mechanism it would be expected that increasing OC content would lead to longer diffusion pathlengths and, consequently, to smaller rate constants. In addition, it was tested whether differential scanning calorimetry would reveal a glass transition in the soils/sediments. In spite of the sensitivity of the equipment used (changes in heat flow in the micro-Watt range were measurable), a glass transition was not observed. This means that activation enthalpies of slow desorption can be calculated from desorption measurements at various temperatures. In the present study these values ranged from 60 to 100 kJ/mol among the various soils and sediments studied.     

臭氧氧化法处理焦化废水生化出水的反应动力学

对臭氧氧化去除焦化废水生化出水COD的反应动力学及其影响因素进行了实验研究,结果表明,在臭氧投加量为8．50mg／min,反应温度为20＇E和初始pH为10．61条件下,对COD的降解符合表观一级反应动力学模型,其相关系数R。=0．9991,表观反应速率常数k。。=1．01×10^-3s-1。该条件下,臭氧氧化对COD的降解主要来源于高活性羟基自由基的强氧化作用。在不同的臭氧投加量（4．25～12．75mg／min）、不同的反应温度（10～40℃）和不同的初始pH（3．76～12．53）下,COD的降解也同样遵循一级反应动力学规律。随着臭氧投加量的增大,COD降解的表观反应速率常数从（0．554×10^-3）s-1增加到（1．06×10＆-3）s-1;随着反应温度的升高,表观反应速率常数从（0．427×10^-3）s-1增加到（1．40×10-3）s-1,温度越高反应速率提高的幅度却越小;在初始pH3．76～10．61范围内,表观反应速率常数从（0．218×10^-3）s-1增加到（1．01×10^-3）s-1,在初始pH为12．53时表观反应速率常数下降到（0．857×10^-3）s-1。     

Ferrate(VI): green chemistry oxidant for degradation of cationic surfactant

Iron in its familiar form exists in the +2 and +3 oxidation states, however, higher oxidation state of iron +6, ferrate(VI) (Fe(VI)O(4)(2-)) can be obtained. The high oxidation power of ferrate(VI) can be utilized in developing cleaner ("greener") technology for remediation processes. This paper demonstrates the unique property of ferrate(VI) to degrade almost completely the cationic surfactant, cetylpyridinium chloride (C(5)H(5)N(+)(CH(2))(15)CH(3).H(2)O Cl(-), CPC). The Rate law for the oxidation of CPC by ferrate(VI) at pH 9.2 was found to be: -d[Fe(VI)]/dt = k[Fe(VI)][CPC](2). Ferrate(VI) oxidizes CPC within minutes and molar consumption of ferrate(VI) was nearly equal to the oxidized CPC. The decrease in total organic carbon (TOC) from CPC was more than 95%; suggesting mineralization of CPC to carbon dioxide. Ammonium ion was the other product of the oxidation. This is the first report in which Fe(VI)O(4)(2-) ion opens the pyridine ring and mineralizes the aliphatic chain of the organic molecule giving inorganic ions.     

TS-1分子筛催化O3/H2O2氧化乙酸

研究了酸性条件下TS-1分子筛催化O3/H2O2体系(O3/H2O2/TS-1)对降解水中乙酸效率的影响,优化了相关工艺参数,并对其作用机理进行了分析。结果表明,在pH为2.8时,TS-1的加入能显著提高臭氧化的降解效率。优化工艺参数表明,当过氧化氢投加量为3 g/L,TS-1投加量为5 g/L时,O3/H2O2/TS-1体系对乙酸具有较高的降解率,60 min后O3/H2 O2/TS-1体系对乙酸(初始浓度为100 mg/L)的去除率达到了58.7%。当pH为0.8时,O3/H2 O2/TS-1体系对乙酸的去除率仅为19.8%,降解效果较差。定量化计算表明,O3/H2O2和O3/H2O2/TS-1的Rct分别为1.62×10-8和8.67×10-7。通过测定乙酸降解过程水样中过氧化氢和液相臭氧的浓度变化,推测了具体反应机理。由于此体系在酸性条件下对乙酸有较好的降解效果,拓宽了现有O3/H2O2体系的应用范围。     

膜吸收法处理高浓度甲醛废气资源化技术研究

采用疏水性中空纤维膜接触器,以NaHSO₃为吸收液处理高浓度甲醛废气。研究了吸收液流量、吸收液温度、吸收液浓度、气体进口流量和气体进口浓度等因素对甲醛去除率和总传质系数的影响。结果表明,当吸收液流量为4.17×10^-6m³/s,吸收液温度为60℃,甲醛进气流量为3.7×10^-6m³/s,甲醛进气浓度为566 mg/m³时,甲醛出气浓度可低至2.8 mg/m³,甲醛的去除率可达99.5%,总传质系数为4.46×10^-5m/s。反应产物（ɑ-羟基磺酸钠）易分离,并可作为重要的有机合成原料或用于制备高纯甲醛而得到充分利用,NaHSO₃溶液经适当稀释后仍可作为吸收液循环使用。表明膜吸收法可基本实现高浓度甲醛废气处理的资源化。     

Enhanced chemical oxidation of aromatic hydrocarbons in soil systems

Fenton's destruction of benzene, toluene, ethylbenzene, and xylene (BTEX) was investigated in soil slurry batch reactors. The purpose of the investigation was to quantify the enhancement of oxidation rates and efficiency by varying process conditions such as iron catalyst (Fe(II) or Fe(III); 2, 5, and 10mM), hydrogen peroxide (H2O2; 30, 150, 300 mM), and metal chelating agents (l-ascorbic acid, gallic acid, or N-(2-hydroxyethyl)iminodiacetic acid). Rapid contaminant mass destruction (97% after 3h) occurred in the presence of 300 mM H2O2 and 10 mM Fe(III). An enhanced removal rate (>90% removal after 15 min and 95% removal after 3h) was also observed by combining Fe(III), N-(2-hydroxyethyl)iminodiacetic acid and 300 mM H2O2. The observed BTEX mass removal rate constants (3.6-7.8 x 10(-4)s(-1)) were compared to the estimated rate constants (4.1-10.1 x 10(-3)s(-1)). The influence of non-specific oxidants loss (by reaction with iron hydroxides and soil organic matter) was also explored.     

Effect of ammonium and oxygen on methane and nitrous oxide fluxes across sediment-water interface in a eutrophic lake

Eutrophication has decreased the O(2) content and increased the NH(4)(+) availability in freshwaters. These changes may affect carbon and nitrogen transformation processes and the production of CH(4) and N(2)O, which are important greenhouse gases. We studied release of CH(4) and N(2)O from a eutrophic lake sediment under varying O(2) and NH(4)(+) conditions. Intact sediment cores were incubated in a laboratory microcosm with a continuous anoxic or oxic water flows containing 0, 50, 500, 5,000, or 15000 microM NH(4)(+). With the anoxic flow, the sediment released CH(4), up to 7.9 mmol m(-2)d(-1). With the oxic flow, the CH(4) emissions were small indicating limited CH(4) production and/or effective CH(4) oxidation. Addition of NH(4)(+) did not affect sediment CH(4) release, evidence that the CH(4) oxidizing bacteria were not disturbed by the extra NH(4)(+). The release of N(2)O from the sediment was highest, up to 7.6 micromol m(-2)d(-1), with the oxic flow without NH(4)(+) addition. Oxygen was the key factor regulating the production of NO(3)(-), which enabled denitrification and production of N(2)O. However, the highest NH(4)(+) addition increased nitrification and associated O(2) consumption causing a decrease in sediment O(2) content and in accumulation of NO(3)(-) and N(2)O, which were effectively reduced to N(2) in denitrification. In summary, sediment CH(4) and N(2)O dynamics are regulated more by the availability of O(2) than extra NH(4)(+). Anoxia in eutrophic lakes favouring the CH(4) production, is the major contributor to the atmospheric consequences of water eutrophication.     

Light-induced disappearance of nitrite in the presence of iron (III)

Understanding of rapid disappearance of nitrite in natural waters and its impact on nitrogen natural cycling has remained limited. We found that NO2- disappeared rapidly in pH 3.2 aqueous Fe(III) solutions both in sunlight and in 356 nm light. Quantum yields of the NO2- loss at 356 nm were 0.049-0.14 for initial levels of 10-80 microns NO2- and 200 microns Fe(III). The NO2- loss (at 356 nm) followed apparent first-order kinetics. The rate constants were 1.3 x 10(-3) (40 microns NO2-) and 4.1 x 10(-4) s-1 (80 microns NO2-) for 100 microns Fe(III), and 2.3 x 10(-3) (40 microns NO2-) and 7.5 x 10(-4) s-1 (80 microns NO2(-1)) for 200 microns Fe(III) (t1/2 = 8.7, 27.9, 5.1, and 15.3 min, respectively). The rate constants were directly proportional to [Fe(III)]0 and inversely proportional to [NO2-]0. Agreement between the rate constants obtained experimentally and those calculated mechanistically supports the hypothesis that NO2- was oxidized to NO2 by .OH radicals from photolysis of FeOH2+ complexes, and at high [NO2-]0 (e.g., 80 microns) relative to [Fe(III)]0, hydrolysis of NO2 or N2O4 to form NO3- and NO2- could be significant. This study showed that light and Fe(III)-induced oxidation of NO2- (rate = approximately 10(-1)-10(-2) microns s-1) was more rapid than its direct photolysis (rate = approximately 10(-4) microns s-1), and the photolysis could be a significant source of .OH radicals only in cases where the Fe(III) level is much lower than the NO2- level ([Fe(III)]/[NO2-] < 1/80). This study suggests that the light and Fe(III)-induced oxidation of NO2- would be one potential important pathway responsible for the rapid transformation of NO2- in acidic surface waters, especially those affected by acid-mine drainage or volcanic activities. This study also may be of interest for modeling certain acidic atmospheric water environments.     

Kinetics of oxidation of chlorobenzenes and phenyl-ureas by Fe(II)/H2O2 and Fe(III)/H2O2. Evidence of reduction and oxidation reactions of intermediates by Fe(II) or Fe(III)

The rates of degradation of 1,2,4-trichlorobenzene (TCB), 2,5-dichloronitrobenzene (DCNB), diuron and isoproturon by Fe(II)/H2O2 and Fe(III)/H2O2 have been investigated in dilute aqueous solution ([Organic compound]0 approximately 1 microM, at 25.0 +/- 0.2 degrees C and pH < or = 3). Using the relative rate method with atrazine as the reference compound, and the Fe(II)/H2O2 (with an excess of Fe(II)) and Fe(III)/H2O2 systems as sources of OH radicals, the rate constants for the reaction of OH* with TCB and DCNB were determined as (6.0 +/- 0.3)10(9) and (1.1 +/- 0.2)10(9) M(-1) s(-1). Relative rates of degradation of diuron and isoproturon by Fe(II)/H2O2 were about two times smaller in the absence of dissolved oxygen than in the presence of oxygen. These data indicate that radical intermediates are reduced back to the parent compound by Fe(II) in the absence of oxygen. Oxidation experiments with Fe(III)/H2O2 showed that the rate of decomposition of atrazine markedly increased in the presence of TCB and this increase has been attributed to a regeneration of Fe(II) by oxidation reactions of intermediates (radical species and dihydroxybenzenes) by Fe(III).     

Atmospheric fate of acrylic acid and acrylonitrile: Rate constants with Cl atoms and OH radicals in the gas phase

Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with acrylic acid and acrylonitrile have been determined at 298 K and atmospheric pressure. The decay of the organics was followed using a gas chromatograph with a flame ionization detector (GC-FID) and the rate constants were determined using a relative rate method with different reference compounds. Room temperature rate constants are found to be (in cm³ molecule⁻¹ s⁻¹): k₁(OH+CH₂CHC(O)OH)=(1.75±0.47)×10⁻¹¹, k₂(Cl+CH₂CHC(O)OH)=(3.99±0.84)×10⁻¹⁰, k₃(OH+CH₂CHCN)=(1.11±0.33)×10⁻¹¹ and k₄(Cl+CH₂CHCN)=(1.11±0.23)×10⁻¹⁰ with uncertainties representing ±2σ. This is the first kinetic study for these reactions under atmospheric pressure. The rate coefficients are compared with previous determinations taking into account the effect of pressure on the rate constants. The effect of substituent atoms or groups on the overall rate constants is analyzed in comparison with other unsaturated compounds in the literature. In addition, atmospheric lifetimes based on the homogeneous sinks of acrylic acid and acrylonitrile are estimated and compared with other tropospheric sinks for these compounds.     

Evaluation of mutagenic potential of contaminated atmosphere at Ibirapuera Park, São Paulo - SP, Brazil, using the Tradescantia stamen-hair assay

We report seasonal variation in CH(4) and N(2)O emission rate from solid storage of bovine manure in Delhi as well as emission factors and emission inventory from manure management systems in India. Emission flux observed in the year 2002-2003 was 4.29+/-1, 4.84+/-2.44 and 12.92+/-4.25 mg CH(4)kg(-1)dung day(-1), as well as 31.29+/-4.93, 72.11+/-16.22 and 6.39+/-1.76 microgN(2)O kg(-1)dung day(-1) in winter, summer and rainy seasons, respectively. CH(4) emission factors varied from 0.8 to 3.3 kg hd(-1)year(-1) for bovines and were lower than IPCC-1996 default values. N(2)O emission factors varied from 3 to 11.7 mg hd(-1)year(-1) from solid storage of manure. Inventory estimates were found to about 698+/-27 Gg CH(4) from all manure management systems and 2.3+/-0.46 tons of N(2)O from solid storage of manure for the year 2000.     

Fluxes of N2O, CH4 and CO2 in a meadow ecosystem exposed to elevated ozone and carbon dioxide for three years

Open-top chambers (OTCs) were used to evaluate the effects of moderately elevated O3 (40-50 ppb) and CO2 (+100 ppm) and their combination on N2O, CH4 and CO2 fluxes from ground-planted meadow mesocosms. Bimonthly measurements in 2002-2004 showed that the daily fluxes of N2O, CH4 and CO2 reacted mainly to elevated O3, while the fluxes of CO2 also responded to elevated CO2. However, the fluxes did not show any marked response when elevated O3 and CO2 were combined. N2O and CO2 emissions were best explained by soil water content and air and soil temperatures, and they were not clearly associated with potential nitrification and denitrification. Our results suggest that the increasing O3 and/or CO2 concentrations may affect the N2O, CH4 and CO2 fluxes from the soil, but longer study periods are needed to verify the actual consequences of climate change for greenhouse gas emissions.     

TS-1分子筛催化O_3/H_2O_2氧化乙酸

研究了酸性条件下TS-1分子筛催化O3/H2O2体系（O3/H2O2/TS-1）对降解水中乙酸效率的影响,优化了相关工艺参数,并对其作用机理进行了分析。结果表明,在pH为2.8时,TS-1的加入能显著提高臭氧化的降解效率。优化工艺参数表明,当过氧化氢投加量为3 g/L,TS-1投加量为5 g/L时,O3/H2O2/TS-1体系对乙酸具有较高的降解率,60 min后O3/H2 O2/TS-1体系对乙酸（初始浓度为100 mg/L）的去除率达到了58.7%。当pH为0.8时,O3/H2 O2/TS-1体系对乙酸的去除率仅为19.8%,降解效果较差。定量化计算表明,O3/H2O2和O3/H2O2/TS-1的Rct分别为1.62×10-8和8.67×10-7。通过测定乙酸降解过程水样中过氧化氢和液相臭氧的浓度变化,推测了具体反应机理。由于此体系在酸性条件下对乙酸有较好的降解效果,拓宽了现有O3/H2O2体系的应用范围。     

Degradation of octylphenol and nonylphenol by ozone - part I: direct reaction

This aqueous reaction between ozone and two alkylphenols (APs), namely octylphenol (OP) and nonylphenol (NP), has been investigated. Both compounds are important endocrine disrupting chemicals, which arise from the biodegradation of alkylphenol ethoxylates and are often found at relatively high concentrations in wastewater effluents. In this paper the results of an experimental study are presented which provide values for the reaction rate constants between molecular ozone and undissociated OP and NP, and overall reaction rate constants for the degradation of the two APs at pH values in the range of 7-9. The kinetic rate constants for OP and NP degradation by molecular ozone were 4.33(+/-0.18) x 10(4) and 3.90(+/-0.10) x 10(4) M(-1) s(-1), and the reaction stoichiometry was similar in both cases and equal to approximately 1.3:1 ([O3]:[AP]). The overall second order reaction rate constants for the two APs increased significantly with increasing pH, which is believed to be mainly due to the increasing influence of indirect radical reaction with increasing pH; this aspect is considered in more detail in a companion paper. A preliminary investigation of the reaction mechanism suggests that an initial product of ozonation is hydroxyl-alkyl phenol.     

FTIR gas-phase kinetic study on the reactions of some acrylate esters with OH radicals and Cl atoms

Acrylate esters are α,β-unsaturated esters that contain vinyl groups directly attached to the carbonyl carbon. These compounds are widely used in the production of plastics and resins. Atmospheric degradation processes of these compounds are currently not well understood. The kinetics of the gas phase reactions of OH radicals with methyl 3-methylacrylate and methyl 3,3-dimethylacrylate were determined using the relative rate technique in a 50 L Pyrex photoreactor using in situ FTIR spectroscopy at room temperature (298?±?2 K) and atmospheric pressure (708?±?8 Torr) with air as the bath gas. Rate coefficients obtained were (in units cm³ molecule^?1 s^?1): (3.27?±?0.33)?×?10^?11 and (4.43?±?0.42)?×?10^?11, for CH₃CH═CHC(O)OCH₃ and (CH₃)₂CH═CHC(O)OCH_3, respectively. The same technique was used to study the gas phase reactions of hexyl acrylate and ethyl hexyl acrylate with OH radicals and Cl atoms. In the experiments with Cl, N₂ and air were used as the bath gases. The following rate coefficients were obtained (in cm³ molecule^?1 s^?1): k₃ (CH₂═CHC(O)O(CH₂)₅CH₃?+?Cl)?=?(3.31?±?0.31)?×?10^?10, k₄(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?Cl)?=?(3.46?±?0.31)?×?10^?10, k₅(CH₂═CHC(O)O(CH₂)₅CH₃?+?OH)?=?(2.28?±?0.23)?×?10^?11, and k₆(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?OH)?=?(2.74?±?0.26)?×?10^?11. The reactivity increased with the number of methyl substituents on the double bond and with the chain length of the alkyl group in –C(O)OR. Estimations of the atmospheric lifetimes clearly indicate that the dominant atmospheric loss process for these compounds is their daytime reaction with the hydroxyl radical. In coastal areas and in some polluted environments, Cl atom-initiated degradation of these compounds can be significant, if not dominant. Maximum Incremental Reactivity (MIR) index and global warming potential (GWP) were also calculated, and it was concluded that these compounds have significant MIR values, but they do not influence global warming.     

Chemical oxidative degradation of methyl tert-butyl ether in aqueous solution by Fenton's reagent

Degradation of methyl tert-butyl ether (MTBE) in aqueous solution by Fenton's reagent (Fe2+ and H2O2) was investigated. Effects of reaction conditions on the oxidation efficiency of MTBE by Fenton's reagent were examined in batch experiments. Under optimum conditions, 15 mM H2O2, 2 mM Fe2+, pH 2.8 and room temperature, the initial 1 mM MTBE solution was reduced by 99% within 120 min. Results showed that MTBE was decomposed in a two-stage reaction. MTBE was first decomposed swiftly based on a Fe2+/H2O2 reaction and then decomposed somewhat less rapidly based on a Fe3+/H2O2 reaction. The detection of Fe2+ also supported the theory of the two-stage reaction for the oxidation of MTBE by Fenton's reagent. The dissolved oxygen in the solution decreased rapidly in the first stage reaction, but it showed a slow increase in the second stage with a zero-order kinetics. A reaction mechanism involving two different pathways for the decomposition of MTBE by Fenton's reagent was also proposed. Chemicals including tert-butyl formate, tert-butyl alcohol, methyl acetate and acetone were identified to be the primary intermediates and by-products of the degradation processes.     

Methylmercury production in the water column of an ultraoligotrophic lake of Northern Patagonia, Argentina

Methyl-mercury (CH3Hg+) production was studied in freshwaters from lake Moreno, an ultraoligotrophic system belonging to Northern Patagonia. Hg2+ labelled with high specific activity 197Hg was spiked to water samples in concentrations of 10 ng l(-1), and incubated in laboratory for 3d time trends under different conditions. Experimental water was sampled daily to evaluate CH3(197)Hg+ production. Lake water used in the experiments was sampled just below the upper limit of the metalimnion ( approximately 30 m depth), where maximum values of chlorophyll a have been measured previously. Sampling was performed in late autumn, when the plankton fraction <50 microm exhibited mercury concentrations up to 260 microg g(-1) dry weight. The experiments analysed lake water filtered through 50, 20, and 0.2 microm (filter-sterilized) mesh nets. ASTM grade 1 water was also incubated for control. All the experiments were run in an environmental chamber under controlled temperature and light regime. High Hg2+ conversion to CH3Hg+, up to 50%, was measured in lake water, in a process stimulated by light. CH3Hg+ production was two-fold higher after 3d of incubation with illumination compared to total darkness. Sterile lake water showed conversions up to 30%, while the planktonic components seem to enhance the CH3Hg+ production. Overall, our results provide evidence that lake Moreno waters favour CH3Hg+ production in processes stimulated by light. Although biotic components certainly contribute to enhance mercury methylation, water chemistry plays a key role in this process. We hypothesize that dissolved organic matter, particularly its quality, could be decisive.